Reaction Pathways and Intermediates in Selective Ring Opening of Biomass-Derived Heterocyclic Compounds by Iridium

Jenness, Glen R.; Wan, Weiming; Chen, Jingguang G.; Vlachos, Dionisios G.

doi:10.1021/acscatal.6b01310

Title: Reaction Pathways and Intermediates in Selective Ring Opening of Biomass-Derived Heterocyclic Compounds by Iridium

Journal Article · Thu Sep 08 00:00:00 EDT 2016 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.6b01310 · OSTI ID:1388770

Jenness, Glen R. ^[1]; Wan, Weiming ^[2]; Chen, Jingguang G. ^[2]; Vlachos, Dionisios G. ^[1]

Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI); Univ. of Delaware, Newark, DE (United States)
Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI); Univ. of Delaware, Newark, DE (United States); Columbia Univ., New York, NY (United States)

While the catalytic hydrogenolysis of biomass-derived aromatic cyclic compounds to functionalized long chain alcohols and polyols has been known for decades, the factors that control the selectivity remain either unknown or controversial. Previous reports have hypothesized full ring saturation of the aromatic ring is necessary prior to hydrogenolysis. Contradictorily, recent studies have shown hydrogenolysis occurs prior to the saturation of the conjugated bonds. Furthermore, it has been assumed the functional groups present are fully reduced prior to hydrogenolysis; however, this has not been shown a priori. In order to resolve these controversies, we combine density functional theory and high-resolution electron energy loss spectroscopy (HREELS) to probe the catalytic hydrogenolysis of saturated and unsaturated heterocyclic molecules (furan, furfural, furfuryl alcohol, and tetrahydrofurfuryl alcohol) on iridium. Our results reveal that full saturation of the aromatic ring is not only unnecessary but leads to slower kinetics and differing selectivities. In contrast to previous studies, we show selective partial ring saturation can enhance the kinetics of the hydrogenolysis process. We report reduction/oxidation of the functional group leads to a change in the electronegativity, resulting in a change in selectivity. These results provide important mechanistic insights allowing for further improvement of catalysts for the effective transformations of biomass-derived oxygenates to value-added products.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of Delaware, Newark, DE (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0001004; AC02-05CH11231

OSTI ID:: 1388770

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 10 Vol. 6; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (46)

Production of High-Quality Diesel from Biomass Waste Products Corma, Avelino; de la Torre, Olalla; Renz, Michael Angewandte Chemie International Edition, Vol. 50, Issue 10 https://doi.org/10.1002/anie.201007508	journal	January 2011
Beyond Petrochemicals: The Renewable Chemicals Industry Vennestrøm, P. N. R.; Osmundsen, C. M.; Christensen, C. H. Angewandte Chemie International Edition, Vol. 50, Issue 45 https://doi.org/10.1002/anie.201102117	journal	October 2011
Nickel Boosts Ring-Opening Activity of Iridium Ziaei-Azad, Hessam; Semagina, Natalia ChemCatChem, Vol. 6, Issue 3 https://doi.org/10.1002/cctc.201300844	journal	January 2014
CC Bond Formation Reactions for Biomass-Derived Molecules Subrahmanyam, Ayyagari V.; Thayumanavan, Sankaran; Huber, George W. ChemSusChem, Vol. 3, Issue 10 https://doi.org/10.1002/cssc.201000136	journal	August 2010
High-Quality Diesel from Hexose- and Pentose-Derived Biomass Platform Molecules Corma, Avelino; de la Torre, Olalla; Renz, Michael ChemSusChem, Vol. 4, Issue 11 https://doi.org/10.1002/cssc.201100296	journal	October 2011
Furfural-A Promising Platform for Lignocellulosic Biofuels Lange, Jean-Paul; van der Heide, Evert; van Buijtenen, Jeroen ChemSusChem, Vol. 5, Issue 1 https://doi.org/10.1002/cssc.201100648	journal	December 2011
Synthesis of High-Quality Diesel with Furfural and 2-Methylfuran from Hemicellulose Li, Guangyi; Li, Ning; Wang, Zhiqiang ChemSusChem, Vol. 5, Issue 10 https://doi.org/10.1002/cssc.201200228	journal	August 2012
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Towards understanding the mechanism for the selective hydrogenation of maleic anhydride to tetrahydrofuran over palladium Pallassana, Venkataraman; Neurock, Matthew; Coulston, George Catalysis Today, Vol. 50, Issue 3-4 https://doi.org/10.1016/S0920-5861(98)00493-3	journal	May 1999
Production of 1,5-pentanediol from biomass via furfural and tetrahydrofurfuryl alcohol Nakagawa, Yoshinao; Tomishige, Keiichi Catalysis Today, Vol. 195, Issue 1 https://doi.org/10.1016/j.cattod.2012.04.048	journal	November 2012
C–O bond hydrogenolysis of cyclic ethers with OH groups over rhenium-modified supported iridium catalysts Chen, Kaiyou; Mori, Kazuma; Watanabe, Hideo Journal of Catalysis, Vol. 294 https://doi.org/10.1016/j.jcat.2012.07.015	journal	October 2012
Ethanol and ethylene glycol on Ni/Pt(111) bimetallic surfaces: A DFT and HREELS study Skoplyak, Orest; Barteau, Mark A.; Chen, Jingguang G. Surface Science, Vol. 602, Issue 23 https://doi.org/10.1016/j.susc.2008.09.040	journal	December 2008
Reaction pathways of furfural, furfuryl alcohol and 2-methylfuran on Cu(111) and NiCu bimetallic surfaces Xiong, Ke; Wan, Weiming; Chen, Jingguang G. Surface Science, Vol. 652 https://doi.org/10.1016/j.susc.2016.02.011	journal	October 2016
Deoxygenation of Biomass-Derived Oxygenates: Reaction of Furfural on Zn-Modified Pt(111) Shi, Daming; Vohs, John M. ACS Catalysis, Vol. 5, Issue 4 https://doi.org/10.1021/acscatal.5b00038	journal	March 2015
Heterogeneous Catalytic Transfer Hydrogenation as an Effective Pathway in Biomass Upgrading Gilkey, Matthew J.; Xu, Bingjun ACS Catalysis, Vol. 6, Issue 3 https://doi.org/10.1021/acscatal.5b02171	journal	January 2016
Adsorption and Reaction of Furfural and Furfuryl Alcohol on Pd(111): Unique Reaction Pathways for Multifunctional Reagents Pang, Simon H.; Medlin, J. Will ACS Catalysis, Vol. 1, Issue 10 https://doi.org/10.1021/cs200226h	journal	August 2011
Catalytic Reduction of Biomass-Derived Furanic Compounds with Hydrogen Nakagawa, Yoshinao; Tamura, Masazumi; Tomishige, Keiichi ACS Catalysis, Vol. 3, Issue 12 https://doi.org/10.1021/cs400616p	journal	October 2013
Iridium- and Platinum-Free Ring Opening of Indan Shen, Jing; Semagina, Natalia ACS Catalysis, Vol. 4, Issue 1 https://doi.org/10.1021/cs400986v	journal	December 2013
Total Hydrogenation of Furfural and 5-Hydroxymethylfurfural over Supported Pd–Ir Alloy Catalyst Nakagawa, Yoshinao; Takada, Kana; Tamura, Masazumi ACS Catalysis, Vol. 4, Issue 8 https://doi.org/10.1021/cs500620b	journal	July 2014
Molecular Orbital View of Chemisorbed Carbon Monoxide Blyholder, George The Journal of Physical Chemistry, Vol. 68, Issue 10 https://doi.org/10.1021/j100792a006	journal	October 1964
Chains of trans-edge-sharing molybdenum octahedra: metal-metal bonding in extended systems Hughbanks, Timothy; Hoffmann, Roald Journal of the American Chemical Society, Vol. 105, Issue 11 https://doi.org/10.1021/ja00349a027	journal	June 1983
Experimental and Theoretical Investigation of the Stability of Pt−3d−Pt(111) Bimetallic Surfaces under Oxygen Environment Menning, Carl A.; Hwu, Henry H.; Chen, Jingguang G. The Journal of Physical Chemistry B, Vol. 110, Issue 31 https://doi.org/10.1021/jp061697z	journal	August 2006
Direct Transformation of Furfural to 1,2-Pentanediol Using a Hydrotalcite-Supported Platinum Nanoparticle Catalyst Mizugaki, Tomoo; Yamakawa, Takayuki; Nagatsu, Yuki ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 10 https://doi.org/10.1021/sc500325g	journal	September 2014
The hydrodeoxygenation of bioderived furans into alkanes Sutton, Andrew D.; Waldie, Fraser D.; Wu, Ruilian Nature Chemistry, Vol. 5, Issue 5, p. 428-432 https://doi.org/10.1038/nchem.1609	journal	April 2013
Selective deoxygenation of sugar polyols to α,ω-diols and other oxygen content reduced materials—a new challenge to homogeneous ionic hydrogenation and hydrogenolysis catalysis Schlaf, Marcel Dalton Trans., Issue 39 https://doi.org/10.1039/B608007C	journal	January 2006
A DFT study of furan hydrogenation and ring opening on Pd(111) Wang, Shengguang; Vorotnikov, Vassili; Vlachos, Dionisios G. Green Chem., Vol. 16, Issue 2 https://doi.org/10.1039/C3GC41183D	journal	January 2014
One-pot selective conversion of furfural into 1,5-pentanediol over a Pd-added Ir–ReO _x /SiO ₂ bifunctional catalyst Liu, Sibao; Amada, Yasushi; Tamura, Masazumi Green Chem., Vol. 16, Issue 2 https://doi.org/10.1039/C3GC41335G	journal	January 2014
Advances in conversion of hemicellulosic biomass to furfural and upgrading to biofuels Dutta, Saikat; De, Sudipta; Saha, Basudeb Catalysis Science & Technology, Vol. 2, Issue 10 https://doi.org/10.1039/c2cy20235b	journal	January 2012
Production of high quality diesel from cellulose and hemicellulose by the Sylvan process: catalysts and process variables Corma, Avelino; de la Torre, Olalla; Renz, Michael Energy & Environmental Science, Vol. 5, Issue 4 https://doi.org/10.1039/c2ee02778j	journal	January 2012
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22 https://doi.org/10.1063/1.1323224	journal	December 2000
Comparison of methods for finding saddle points without knowledge of the final states Olsen, R. A.; Kroes, G. J.; Henkelman, G. The Journal of Chemical Physics, Vol. 121, Issue 20 https://doi.org/10.1063/1.1809574	journal	November 2004
Efficient methods for finding transition states in chemical reactions: Comparison of improved dimer method and partitioned rational function optimization method Heyden, Andreas; Bell, Alexis T.; Keil, Frerich J. The Journal of Chemical Physics, Vol. 123, Issue 22 https://doi.org/10.1063/1.2104507	journal	December 2005
Experimental and theoretical study of reactivity trends for methanol on Co∕Pt(111) and Ni∕Pt(111) bimetallic surfaces Skoplyak, Orest; Menning, Carl A.; Barteau, Mark A. The Journal of Chemical Physics, Vol. 127, Issue 11 https://doi.org/10.1063/1.2768520	journal	September 2007
Superlinearly converging dimer method for transition state search Kästner, Johannes; Sherwood, Paul The Journal of Chemical Physics, Vol. 128, Issue 1 https://doi.org/10.1063/1.2815812	journal	January 2008
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen Dunning, Thom H. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456153	journal	January 1989
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 111, Issue 15 https://doi.org/10.1063/1.480097	journal	October 1999
Coordination and reaction mechanism of furan on Ru(001) Yan, F. Q.; Qiao, M. H.; Wei, X. M. The Journal of Chemical Physics, Vol. 111, Issue 17 https://doi.org/10.1063/1.480140	journal	November 1999
Electronic structure calculations with GPAW: a real-space implementation of the projector augmented-wave method Enkovaara, J.; Rostgaard, C.; Mortensen, J. J. Journal of Physics: Condensed Matter, Vol. 22, Issue 25 https://doi.org/10.1088/0953-8984/22/25/253202	journal	June 2010
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Localized atomic basis set in the projector augmented wave method Larsen, A. H.; Vanin, M.; Mortensen, J. J. Physical Review B, Vol. 80, Issue 19 https://doi.org/10.1103/PhysRevB.80.195112	journal	November 2009
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
1,5-Pentanediol Kaufman, Daniel; Reeve, Wilkins Organic Syntheses, Vol. 26, p. 83 https://doi.org/10.15227/orgsyn.026.0083	journal	January 1946

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Metal Catalysts for the Efficient Transformation of Biomass-derived HMF and Furfural to Value Added Chemicals Gupta, Kavita; Rai, Rohit K.; Singh, Sanjay K. ChemCatChem, Vol. 10, Issue 11 https://doi.org/10.1002/cctc.201701754	journal	March 2018
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
HREELS
Ir
bio-inspired
biofuels (including algae and biomass)
catalysis (heterogeneous)
catalysis (homogeneous)
density functional theory
diol
furfural
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hydrogen and fuel cells
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ring opening
synthesis (novel materials)
synthesis (scalable processing)
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Title: Reaction Pathways and Intermediates in Selective Ring Opening of Biomass-Derived Heterocyclic Compounds by Iridium

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